Image reversal negative working O-naphthoquinone diazide and cross-linking compound containing photoresist process with thermal curing

ABSTRACT

A process for converting a normally positive working photosensitive composition to a negative working composition is disclosed. One forms a composition containing an alkali soluble resin, a 1,2 quinone diazide-4-sulfonyl compound and an acid catalyzed crosslinker in a solvent mixture. After drying and imagewise exposing, the composition is baked and developed to produce a negative image. The image-reversal negative-working photoresists of this invention have superior storage stability and shelf life.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation of co-pending U.S. patent application Ser. No.07/530,544 filed May 25, 1990, now abandoned which was acontinuation-in-part of U.S. patent application Ser. No. 07/268,639filed on Nov. 8, 1988, U.S. Pat. No. 4,929,536 granted May 29, 1990,which was a continuation of U.S. patent application Ser. No. 06/895,609,filed Aug. 11, 1986, now abandoned, which was a continuation-in-part ofU.S. patent application Ser. No. 889,032 filed on Jul. 23, 1986, nowabandoned, which was a continuation-in-part of U.S. patent applicationSer. No. 764,700 filed on Aug. 12, 1985, now abandoned, all of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates generally to radiation sensitivephotoresist compositions and particularly to compositions containingaqueous alkali soluble resins together with naphthoquinone diazidesensitizing agents.

It is well known in the art to produce positive photoresist formulationssuch as those described in U.S. Pat. Nos. 3,666,473, 4,115,128,4,173,470 and 4,550,069. These include alkali solublephenol-formaldehyde novolak resins together with light sensitivematerials, usually a substituted naphthoquinone diazide compound. Theresins and sensitizers are dissolved in an organic solvent or mixture ofsolvents and are applied as a thin film or coating to a substratesuitable for the particular application desired.

The resin component of these photoresist formulations is soluble inaqueous alkaline solutions, but the naphthoquinone sensitizer acts as adissolution rate inhibitor with respect to the resin. Upon exposure ofselected areas of the coated substrate to actinic radiation, however,the sensitizer undergoes a radiation induced structural transformationand the exposed areas of the coating are rendered more soluble than theunexposed areas. This difference in solubility rates causes the exposedareas of the photoresist coating to be dissolved when the substrate isimmersed in an alkaline developing solution while the unexposed areasare largely unaffected, thus producing a positive relief pattern on thesubstrate.

In most instances, the exposed and developed substrate will be subjectedto treatment by a substrate-etchant solution. The photoresist coatingprotects the coated areas of the substrate from the etchant and thus theetchant is only able to etch the uncoated areas of the substrate, whichin the case of a positive photoresist, correspond to the areas that wereexposed to actinic radiation. Thus, an etched pattern can be created onthe substrate which corresponds to the pattern on the mask, stencil,template, etc., that was used to create selective exposure patterns onthe coated substrate prior to development.

The relief pattern of the photoresist on substrate produced by themethod described above is useful for various applications including asan exposure mask or a pattern such as is employed in the manufacture ofminiaturized integrated electronic components.

The properties of a photoresist composition which are important incommercial practice include the photospeed of the resist, developmentcontrast, resist resolution, and resist adhesion.

Resist resolution refers to the capacity of a resist system to reproducethe smallest equally spaced line pairs and intervening spaces of a maskwhich is utilized during exposure with a high degree of image edgeacuity in the developed exposed spaces. In many industrial applications,particularly in the manufacture of miniaturized electronic components, aphotoresist is required to provide a high degree of resolution for verysmall line and space widths (on the order of one micron or less).

The ability of a resist to reproduce very small dimension, on the orderof a micron or less, is extremely important in the production of largescale integrated circuits on silicon chips and similar components.Circuit density on such a chip can only be increased, assumingphotolithography techniques are utilized, by increasing the resolutioncapabilities of the resist.

Photoresists are generally categorized as being either positive workingor negative working. In a negative working resist composition, theimagewise light struck areas harden and form the image areas of theresist after removal of the unexposed areas with a developer. In apositive working resist the exposed areas are the non-image areas. Thelight struck parts are rendered soluble in aqueous alkali developers.While negative resists are the most widely used for industrialproduction of printed circuit boards, positive resists are capable ofmuch finer resolution and smaller imaging geometries. Hence positiveresists are the choice for the manufacture of densely packed integratedcircuits.

In many commercial application, it is desirable to convert a highresolution quinone diazide type positive resist for a negative workingapplication. There is interest in the field of image reversal because ofthe utility of this process in practical device manufacturing. Among thepractical aspects of image reversal are the elimination of the need fora dual set of complementary masks to do both positive and negativeimaging, greater resolution and process latitude than with positiveimaging alone, reduction in standing wave effects, and higher thermalstability. In this regard, several methods have been suggested for suchimage reversal. See for example: "Image Reversal: The Production of aNegative Image in a Positive Photoresist" by S. A. MacDonald et al. p.114, IBM Research Disclosure, 1982; "Image Reversal of PositivePhotoresist". A New Tool for Advancing Integrated Circuit Fabrication"by E. Alling et al., Journal of the Society of Photo-Imaging Engineers,Vol. 539, p.194, 1985; M. V. Buzuev et.al. "Producing a Negative Imageon a Positive Photoresist" SU 1,109,708; German Patent DE 52 9054, C2,1975, Assigned to H. Moritz and G. Paal, Making a Negative Image; andU.S. Pat. No. 4,104,070.

Each of these disclosures suffer from several drawbacks. A majordisadvantage of current image reversal processes is the need for anadditional processing step which involves treatment with either saltforming compounds or high energy exposure sources such as electronbeams. The present invention provides a mechanism which involves theformation of a catalytic amount of a photogenerated acid which crosslinks the resin in the exposed region.

The invention provides a unique chemical composition, which whenprocessed in a slightly modified manner to the usual and customarymethod of lithographic processing, yields a totally unexpected negative,reversed tone image from an otherwise expected positive typephotosensitizer.

Among the advantages realized by this highly desirable result areimprovement in the relationship between exposure energy and resultingline width, improved process latitude, improvement in developed imageresolution, substantial elimination of reflective notching, enhancedphotosensitivity, improved thermal stability of the resulting image,improved adhesion between the photoresist and commonly used substrates,and superior storage stability and shelf life of the photoresist.

SUMMARY OF THE INVENTION

A process for converting a normally positive working photosensitivecomposition to a negative working composition is disclosed. One forms acomposition containing an alkali soluble resin, 1,2 quinonediazide-4-sulfonyl compound and an acid catalyzed crosslinker in asolvent mixture. After drying and imagewise exposing, the composition isbaked and developed to produce a negative image. The image-reversalnegative-working photoresists of this invention have superior storagestability and shelf life.

The invention provides a process for preparing a negative workingphotographic element which comprises in order:

a) forming a composition which comprises

i) from about 1% to about 25% based on the weight of the solid parts ofthe composition of a photosensitive compound having the formula ##STR1##wherein R₁ =1,2 benzoquinone-2-diazide-4-sulfonyl;

1,2 naphthoquinone-2-diazide-4-sulfonyl; or

1,2 anthraquinone-2-diazide-4-sulfonyl;

R₂ =H, R₇, OR₆ or ##STR2## R₃ =H, R₇, OR₆ or ##STR3## R₄ =H, R₇, OR₆ or##STR4## R₆ =H, alkyl, aryl, aralkyl or R₁ R₇ =alkyl, aryl or aralkyl

ii) from about 75% to about 99% based on the weight of the solid partsof the composition of a novolak and/or polyvinyl phenol resin; and

iii) from about 0.5% to about 20% based on the weight of the solid partsof the composition of a crosslinking compound which, when in thepresence of that amount and strength of the acid generated when saiddiazide is exposed to actinic radiation, is capable of crosslinking saidresin under the application of the heating conditions of step (e), saidcrosslinking compound has the formula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO--₂,--O--CO₂ --, CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl,cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄are independently H, C₁ -C₄ -alkyl or substituted or unsubstitutedphenyl and n ranges from 1 to 3 and m ranges from 0-3, provided that n+mis greater than 1; and

iv) sufficient solvent to dissolve the foregoing composition components;and

b) coating said composition on a suitable substrate; and

c) heating said coated substrate at a temperature of from about 20° C.to about 100° C. until substantially all of said solvent is dried off;and

d) imagewise exposing said composition to actinic, electron beam, ionbeam or x-ray radiation; and

e) heating said coated substrate at a temperature of at least about 95°C. to about 160° C. for from about 10 seconds or more to crosslink saidresin; then optionally flood exposing the composition overall to actinicradiation in the range of from about 200 to about 500 nm in an amountsufficient to react said coating; and

f) removing the unexposed non-image areas of said composition with asuitable developer.

According to the present invention there is provided: a process forpreparing a negative working photographic element which comprises inorder:

a) forming a composition which comprises

i) from about 1% to about 25% based on the weight of the solid parts ofthe composition of a photosensitive compound represented by the generalformulae (1), (2), (3): ##STR5## wherein R is H, --X--R_(b) or ##STR6##X is a single C--C bond, --O--, --S--, --SO₂ --, ##STR7## in is 1 or 2,R_(a) is H, --OH, --OY, --OZ, halogen or lower alkyl, with at least oneR_(a) radical being --OY and at least one thereof being --OZ, R_(b) isH, alkyl, aryl, substituted alkyl, or substituted aryl; ##STR8## whereinR₁ is H, or ##STR9## Rc is H, --OH, --OY or --OZ, with at least oneR_(c) radical being --OY and at least one thereof being --OZ; and##STR10## wherein R₂ is H, alkyl, aryl, substituted alkyl, orsubstituted aryl, R_(d) is --OH, --OY or --OZ with at least one R_(d)radical being --OY and at least one thereof being --OZ;

wherein Y is 1,2-naphthoquinone-diazide-4-sulfonyl and Z is1,2-naphthoquinone-diazide-5-sulfonyl or --W--R₃,

where W is ##STR11## or SO₂ --, and R₃ is alkyl, aryl, substituted alkylor substituted aryl;

ii) from about 75% to about 99% based on the weight of the solid partsof the composition of a novolak and/or polyvinyl phenol resin; and

iii) from about 0.5% to about 20% based on the weight of the solid partsof the composition of a crosslinking compound which, when in thepresence of that amount and strength of the acid generated when saiddiazide is exposed to actinic radiation, is capable of crosslinking saidresin under the application of the heating conditions of step (e), saidcrosslinking compound has the formula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO₂,--O--CO₂ --, --CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl,cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄are independently H, C₁ -C₄ -alkyl or substituted or unsubstitutedphenyl and n ranges from 1 to 3 and m ranges from 0-3, provided that n+mis greater than 1; and

iv) sufficient solvent to dissolve the foregoing composition components;and

b) coating said composition on a suitable substrate; and

c) heating said coated substrate at a temperature of from about 20° C.to about 100° C. until substantially all of said solvent is dried off;and

d) imagewise exposing said composition to actinic, electron beam, ionbeam or x-ray radiation; and

e) heating said coated substrate at a temperature of at least about 95°C. to about 160° C. for from about 10 seconds or more to crosslink saidresin; then optionally flood exposing the composition overall to actinicradiation in the range of from about 200 to about 500 nm in an amountsufficient to react said coating; and

f) removing the unexposed non-image areas of said compositions with asuitable developer.

According to the present invention there is provided: a process forpreparing a negative working photographic element which comprises inorder:

a) forming a composition which comprises

i) from about 1% to about 25% based on the weight of the solid parts ofthe photosensitizer composition comprising the condensation product of:

(I) a phenolic compound selected from the group consisting of: ##STR12##wherein R is H, --X--R_(b) or ##STR13## R_(a) is H, --OH, halogen orlower alkyl, with at least two and not greater than six R_(a) radicalsbeing --OH, X is a single C--C bond, --O--, --S--, --SO₂ --, ##STR14## nis 1 or 2, R_(b) is H, alkyl, aryl, substituted alkyl or substitutedaryl; ##STR15## wherein R₁ is H or ##STR16## R_(c) is H or --OH with atleast two R_(c) radicals being --OH; and ##STR17## wherein R₂ is H,alkyl, aryl, substituted alkyl, or substituted aryl;

(II) a 1,2-naphthoquinonediazide-4-sulfonic acid (Diazo 1); and

(III) a 1,2-naphthoquinonediazide-5-sulfonic acid (Diazo 2) and/or anorganic acid halide represented by the formula:

    W--R.sub.3

wherein W is ##STR18## or --SO₂ --V, V is halogen, R3 is alkyl, aryl,substituted alkyl, or substituted aryl;

wherein the molar ration of the amount of Diazo 1 reacted to the amountof Diazo 2 and/or organic acid reacted is in the range of from about 1:1to about 39:1:

ii) from about 75% to about 99% based on the weight of the solid partsof the composition of a novolak and/or polyvinyl phenol resin; and

iii) from about 0.5% to about 20% based on the weight of the solid partsof the composition of a crosslinking compound which, when in thepresence of that amount and strength of the acid generated when saiddiazide is exposed to actinic radiation, is capable of crosslinking saidresin under the application of the heating conditions of step (e), saidcrosslinking compound has the formula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO₂,--O--CO₂ --, --CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl,cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄are independently H, C₁ -C₄ -alkyl or substituted or unsubstitutedphenyl and n ranges from 1 to 3 and m ranges from 0-3, provided that n+mis greater than 1; and

iv) sufficient solvent to dissolve the foregoing composition components;and

b) coating said composition on a suitable substrate; and

c) heating said coated substrate at a temperature of from about 20° C.to about 100° C. until substantially all of said solvent is dried off;and

d) imagewise exposing said composition to actinic, electron beam, ionbeam or x-ray radiation; and

e) heating said coated substrate at a temperature of at least about 95°C. to about 160° C. for from about 10 seconds or more to crosslink saidresin; then optionally flood exposing the composition overall to actinicradiation in the range of from about 200 to about 500 nm in an amountsufficient to react said coating; and

f) removing the unexposed non-image areas of said compositions with asuitable developer.

The invention also provides a composition which comprises

i) from about 1% to about 25% based on the weight of the solid parts ofthe composition of a photosensitive compound having the formula##STR19## wherein R₁ =1,2 benzoquinone-2-diazide-4 -sulfonyl;

1,2 naphthoquinone-2-diazide-4-sulfonyl; or

1,2 anthraquinone-2-diazide-4-sulfonyl

R₂ =H, R₇, OR₆ or ##STR20## R₃ =H, R₇, OR₆ or ##STR21## R₄ =H, R₇, OR₆or ##STR22## R₆ =H, alkyl, aryl, aralkyl or R₁ R₇ =alkyl, aryl oraralkyl

ii) from about 75% to about 99% based on the weight of the solid partsof the composition of a novolak and/or polyvinyl phenol resin; and

iii) from about 0.5% to about 20% based on the weight of the solid partsof the composition of a crosslinking compound which, when in thepresence of that amount and strength of the acid generated when saiddiazide is exposed to actinic radiation, is capable of crosslinking saidresin under the application of heat, said crosslinking compound has theformula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO₂,--O--CO₂ --, CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl,cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄are independently H, C₁ -C₄ -alkyl or substituted or unsubstitutedphenyl and n ranges from 1 to 3 and m ranges from 0-3, provided that n+mis greater than 1; and

iv) sufficient solvent to dissolve the foregoing components.

According to the present invention there is provided: a compositionwhich comprises

i) from about 1% to about 25% based on the weight of the solid parts ofthe composition of a photosensitive compound represented by the generalformula (1), (2) or (3): ##STR23## wherein R is H, --X--R_(b) or##STR24## X is a single C--C bond, --O--, --S--, --SO₂ --, ##STR25## nis 1 or 2, R_(a) is H, --OH, --OY, --OZ, halogen or lower alkyl, with atleast one R_(a) radical being --OY and at least one thereof being --OZ,R_(b) is H, alkyl, aryl, substituted alkyl, or substituted aryl;##STR26## wherein R₁ is H, or ##STR27## Rc is H, --OH, --OY or --OZ,with at least one R_(c) radical being --OY and at least one thereofbeing --OZ; and ##STR28## wherein R₂ is H, alkyl, aryl, substitutedalkyl, or substituted aryl, R_(d) is --OH, --OY or --OZ with at leastone R_(d) radicals being --OY and at least one thereof being --OZ;

wherein Y is 1,2-naphthoquinonediazide-4-sulfonyl and Z is1,2-naphthoquinone-diazide-5-sulfonyl or --W--R₃,

where W is ##STR29## or --SO₂ --, and R₃ is alkyl, aryl, substitutedalkyl or substituted aryl:

ii) from about 75% to about 99% based on the weight of the solid partsof the composition of a novolak and/or polyvinyl phenol resin; and

iii) from about 0.5% to about 20% based on the weight of the solid partsof the composition of a crosslinking compound which, when in thepresence of that amount and strength of the acid generated when saiddiazide is exposed to actinic radiation, is capable of crosslinking saidresin under the application of heat said crosslinking compound has theformula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO₂,--O--CO₂ --, CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl,cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄are independently H, C₁ -C₄ -alkyl or substituted or unsubstitutedphenyl and n ranges from 1 to 3 and m ranges from 0-3, provided that n+mis greater than 1; and

iv) sufficient solvent to dissolve the foregoing components.

According to the present invention there is provided: a compositionwhich comprises

i) from about 1% to about 25% based on the weight of the solid parts ofthe composition of a photosensitizer composition comprising thecondensation product of:

(I) a phenolic compound selected from the group consisting of: ##STR30##wherein R is H, --X--R_(b) or ##STR31## R_(a) is H, --OH, halogen orlower alkyl, with at least two and not greater than six R_(a) radicalsbeing --OH, X is a single C--C bond, --O--, --S--, --SO₂ --, ##STR32## nis 1 or 2, R_(b) is H, alkyl, aryl, substituted alkyl or substitutedaryl; ##STR33## wherein R₁ is H or ##STR34## R_(c) is H or --OH with atleast two R_(c) radicals being --OH; and ##STR35## wherein R₂ is H,alkyl, aryl, substituted alkyl, or substituted aryl;

(II) a 1,2-naphthoquinonediazide-4-sulfonic acid (Diazo 1); and

(III) a 1,2-naphthoquinonediazide-5-sulfonic acid (Diazo 2) and/or anorganic acid halide represented by the formula:

    W--R.sub.3

wherein W is ##STR36## or --SO₂ --V, V is halogen, R₃ is alkyl, aryl,substituted alkyl, or substituted aryl;

wherein the molar ratio of the amount of Diazo 1 reacted to the amountof Diazo 2 and/or organic acid reacted is in the range of from about 1:1to about 39:1;

ii) from about 75% to about 99% based on the weight of the solid partsof the composition of a novolak and/or polyvinyl phenol resin; and

iii) from about 0.5% to about 20% based on the weight of the solid partsof the composition of a crosslinking compound which, when in thepresence of that amount and strength of the acid generated when saiddiazide is exposed to actinic radiation, is capable of crosslinking saidresin under the application of heat, said crosslinking compound has theformula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO₂,--O--CO₂ --, --CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl,cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄are independently H, C₁ -C₄ -alkyl or substituted or unsubstitutedphenyl and n ranges from 1 to 3 and m ranges from 0-3, provided that n+mis greater than 1; and

iv) sufficient solvent to dissolve the foregoing components.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

As a first step in the production of the photographic element of thepresent invention, one coats and dries the foregoing photosensitivecomposition on a suitable substrate. The composition contains a solvent,crosslinking agent, binding resin and 1,2 quinone diazide-4-sulfonylgroup containing photosensitizer. The binding resins include the classesknown as the novolaks, polyvinyl phenols and paravinyl phenols.

The production of novolak resins, which may be used for preparingphotosensitive compositions, is well known in the art. A procedure fortheir manufacture is described in Chemistry and Application of PhenolicResins, Knop A. and Scheib, W.; Springer Verlag, New York, 1979 inChapter 4 which is incorporated herein by reference. Polyvinyl phenolsand paravinyl phenols are taught in U.S. Pat. Nos. 3,869,292 and4,439,516, which are incorporated herein by reference. Similarly, theuse of o-quinone diazides is well known to the skilled artisan asdemonstrated by Light Sensitive Systems, Kosar, J.; John Wiley & Sons,New York, 1965 in Chapter 7.4 which is also incorporated herein byreference. These sensitizers which comprise a component of the presentresist compositions of the present invention are preferably selectedfrom the group of substituted naphthoquinone diazide sensitizers whichare conventionally used in the art in positive photoresist formulations.Such sensitizing compounds are disclosed, for example, in U.S. Pat. Nos.2,797,213; 3,106,465; 3,148,983; 3,130,047; 3,785,825; and 3,802,885which are incorporated herein by reference. Other photosensitizers whichmay be used are disclosed in copending U.S. patent application Ser. Nos.858,616 and 859,284, which are incorporated herein by reference.

The photosensitizer is a 1,2 quinone diazide-4-sulfonic acid ester of aphenolic derivative. It presently appears that the number of fused ringsis not important for this invention but the position of the sulfonylgroup is important. That is, one may use benzoquinones, naphthoquinonesor anthroquinones as long as the oxygen is in the 1 position, diazo isin the 2 position and the sulfonyl group is in the 4 position. Likewisethe phenolic member to which it is attached does not appear to beimportant. For example it can be a cumylphenol derivative as taught inU.S. Pat. No. 3,640,992 or it can be a mono-, di-, or tri-hydroxyphenylalkyl ketone or benzophenone as shown in U.S. Pat. No. 4,499,171. Bothof these patents are incorporated herein by reference.

As a generalized formula, the quinone diazides of the present inventionmay be represented by: ##STR37## wherein R₁ =1,2benzoquinone-2-diazide-4-sulfonyl;

1,2 naphthoquinone-2-diazide-4-sulfonyl; or

1,2 anthraquinone-2-diazide-4-sulfonyl;

R₂ =H, R₇, OR₆ or ##STR38## R₃ =H, R₇, OR₆ or ##STR39## R₄ =H, R₇, OR₆or ##STR40## R₆ =H, alkyl, aryl, aralkyl or R₁ R₇ =alkyl, aryl oraralkyl

Useful photosensitizers include (1,2)-naphthoquinonediazide-4-sulfonylchloride, condensed with phenolic compounds such as hydroxybenzophenones especially trihydroxybenzophenone and more particularly2,3,4-trihydroxybenzophenone; 2,3,4-trihydroxyphenyl pentyl ketone1,2-naphthaquinone-2-diazide-4-sulfonic acid trisester or other alkylphenones; 2,3,4-trihydroxy-3'-methoxy benzophenone1,2-naphthaquinone-2-diazide-4-sulfonic acid trisester;2,3,4-trihydroxy-3'-methyl benzophenone1,2-naphthaquinone-2-diazide-4-sulfonic acid trisester; and2,3,4-trihydroxybenzophenone 1,2-naphthoquinonediazide-4-sulfonic acidtrisester.

Other useful photosensitive compounds and photosensitizer compositionsof this invention may be obtained by condensing phenolic compounds witha mixture of Diazo 1 and Diazo 2 and/or organic acid halides. The molarratio of the amount of Diazo 1 to the amount of Diazo 2 and/or organicacid halide in the mixture may be in the range of from about 1:1 toabout 39:1, preferably from about 4:1 to about 19:1, or more preferablyfrom about 93:7 to about 85:15. For example, one mole of2,3,4-trihydroxybenzophenone may be condensed with a 9:1 mixture of 2.7moles of Diazo 1 and 0.3 moles of Diazo 2 to yield a photosensitizercomposition comprising compounds having the formula: ##STR41## where R₁,R₂ and R₃ may independently be either1,2-naphthoquinonediazide-4-sulfonyl or1,2-naphthoquinone-diazide-5-sulfonyl.

The photosensitive compounds may be represented by general formulae (1),(2) and (3): ##STR42## wherein R is H, --X--R_(b) or ##STR43## X is asingle C--C bond, --O--, --S--, --SO₂ --, ##STR44## n is 1 or 2, R_(a)is H, --OH, --OY, --OZ, halogen, preferably Cl or Br, or lower alkyl,preferably lower alkyl having 1-4 carbon atoms, with at least one R_(a)radical being --OY and at least one thereof being --OZ, R_(b) is H,alkyl, aryl, substituted alkyl, or substituted aryl; preferably alkylhaving 1 -20 carbon atoms, more preferably 1-12 carbon atoms, preferablyaryl being phenyl or naphthyl, alkyl or aryl may be substituted withlower alkyl having 1-4 carbon atoms, lower alkoxy having 1-4 carbonatoms, or halogen atoms, preferably Cl or Br; ##STR45## wherein R₁ is Hor ##STR46## R_(c) is H, --OH, --OY, or --OZ, with at least two R_(c)radicals being --OY and at least one thereof being --OZ; and ##STR47##wherein R₂ is H, alkyl, aryl, substituted alkyl, or substituted aryl,R_(d) is --OH, --OY or --OZ with at least one R_(d) radical being --OYand at least one thereof being --OZ; the alkyl radicals R₂ may bestraight-chain or branched and may be substituted with halogen atoms orlower alkoxy groups having 1-4 carbon atoms, preferably the alkylradicals have 1-20 carbon atoms; the aryl radicals R₂ are preferablymononuclear and may be substituted with lower alkyl or alkoxy groupshaving 1-4 carbon atoms or with halogen atoms, preferably the arylradicals have 1 to 10 carbon atoms; compounds in which R₂ is an arylradical are particularly preferred and compounds in which the arylradical is a phenyl radical are especially preferred;

wherein Y is 1,2-naphthoquinonediazide-4-sulfonyl and Z is a1,2-naphthoquinonediazide-5-sulfonyl or --W--R₃,

where W is ##STR48## or --SO₂ --, and R₃ is alkyl, aryl, substitutedalkyl or substituted aryl; the alkyl radicals R₃ may be straight-chainor branched and may be substituted with halogen atoms, preferably Br orCl, or lower alkoxy groups having 1-4 carbons atoms, preferably alkylhaving 1-20 carbon atoms; the aryl radicals R₃ are preferablymononuclear and may be substituted with lower alkyl or alkoxy groupshaving 1-4 carbon atoms or with halogen atoms, preferably Br or Cl,preferably aryl radicals having 6-10 carbon atoms; phenyl radicals arepreferred; alkyl radicals are particularly preferred and lower alkylradicals having 1-6 carbon atoms are especially preferred.

These photosensitive compounds may be prepared, for example, in themanner as herein described for the preparation of the photosensitizercompositions. The compounds may be isolated and purified as desired.

The photosensitizer compositions (comprising inter alia thephotosensitive compounds disclosed herein) may be obtained by condensingphenolic compounds with a mixture of Diazo 1 and Diazo 2 and/or organicacid halides. The Diazo 1 component and the Diazo 2 and/or organic acidhalide component of the mixture may be condensed either sequentially orconcurrently with the phenolic compounds.

The Diazo 1/Diazo 2-organic acid mixture may be reacted preferably instoichiometric quantities with the hydroxyl-bearing compounds. However,the phenol compounds need not be completely esterified and less thanstoichiometric quantities of the Diazo and organic acid halide compoundsmay be condensed with the phenolic compounds provided that the molarration of Diazo 1 to Diazo 2 and/or organic acid halide reacted iswithin the ranges specified herein. The total amount of Diazo 1 andDiazo 2 and/or organic acid halide reacted with the phenolic compoundsshould be sufficient to produce a photosensitizer composition capable ofinhibiting the dissolution rate of an alkali-soluble resin.

The phenolic compounds which may be condensed with the Diazo 1/Diazo2-organic acid mixture are represented by the general formulae (A), (B)and (C): ##STR49## wherein R is H, --X--R_(b) or ##STR50## R_(a) is H,--OH, halogen, preferably Cl or Br, or lower alkyl, preferably loweralkyl having 1 to 4 carbon atoms; with at least two and not greater thansix R_(a) radicals being --OH, X is a single C--C bond, --O--, --S--,--SO₂ --, ##STR51## n is 1 or 2, R_(b) is H, alkyl, aryl, substitutedalkyl or substituted aryl; preferably alkyl having 1-20 carbon atoms,more preferably 1-12 carbon atoms, preferably aryl being phenyl ornaphthyl, alkyl or aryl may be substituted with lower alkyl having 1-4carbon atoms, lower alkoxy having 1-4 carbon atoms, or halogen atoms,preferably Cl or Br; ##STR52## wherein R₁ is H or ##STR53## R_(c) is Hor --OH with at least two R_(c) radicals being --OH; and wherein R₂ isH, alkyl, aryl, substituted alkyl, or substituted aryl; the alkylradicals R₂ may be straight-chain or branched and may be substitutedwith halogen atoms or lower alkoxy groups having 1-4 carbon atoms,preferably the alkyl radicals have 1-20 carbon atoms; the aryl radicalsR₂ are preferably mononuclear and may be substituted with lower alkyl oralkoxy groups having 1-4 carbon atoms or with halogen atoms, preferablythe aryl radicals have 1 to 10 carbon atoms; compounds in which R₂ is anaryl radical are particularly preferred and compounds in which the arylradical is a phenyl radical are especially preferred:

Among the phenolic compounds represented by the general formula (I) are:hydroxyl-bearing benzene compounds such as 1,2-dihydroxy-benzene,1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,2,3-trihydroxybenzene,1,2,4-trihydroxybenzene, 1,3,5-trihydroxybenzene, and the like;dihydroxybenzophenones such as 2,2'-dihydroxybenzophenone,2,3'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone,2,4'-dihydroxybenzophenone, 2,5-dihydroxybenzophenone,3,3'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, and the like;trihydroxybenzophenones such as 2,2',6-trihydroxybenzophenone,2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone,2,4,6-trihydroxybenzophenone, 3,4,5-trihydroxybenzophenone, and thelike; tetrahydroxybenzophenones such as2,2',3,4-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone,2,2',4,6'-tetrahydroxybenzophenone, 2,2',5,6'-tetrahydroxybenzophenone,2,3',4,4'-tetrahydroxybenzophenone, 2,3',4,6-tetrahydroxybenzophenone,2,4,4',6-tetrahydroxybenzophenone, 3,3',4,4'-tetrahydroxybenzophenone,and the like; pentahydroxybenzophenones; hexahydroxybenzophenones;dihydroxy- and trihydroxy-phenyl alkyl ketones such as2,4-dihydroxyphenyl alkyl ketones, 2,5-dihydroxyphenyl alkyl ketones,3,4-dihydroxyphenyl alkyl ketones, 3,5-dihydroxyphenyl alkyl ketones,2,3,4-trihydroxyphenyl alkyl ketones, 3,4,5-trihydroxyphenyl alkylketones, 2,4,6-trihydroxyphenyl alkyl ketones, and the like, preferablyalkyl having 1-12 carbon atoms such as methyl, ethyl, butyl, n-hexyl,heptyl, decyl, dodecyl, and the like, dihydroxyphenyl aralkyl ketones;trihydroxyphenyl aralkyl ketones; dihydroxydiphenyls;trihydroxydiphenyls such as 2,2',4-trihydroxydiphenyl;tetrahydroxydiphenyls such as 2,2',4,4'-tetrahydroxydiphenyl;dihydroxydiphenyl oxides; dihydroxydibenzyl oxides; dihydroxydiphenylalkanes, preferably lower alkanes such as methane, ethane, propane orthe like; dihydroxybenzoic acid; trihydroxybenzoic acids; dihydroxy- andtrihydroxy- benzoic acid alkyl esters, alkyl preferably having 1 to 12carbon atoms, such as n-butyl 2,4-, 2,5-, 3,4- and3,5-dihydroxybenzoate, 2,4,4-trimethylpentyl 2,4-dihydroxybenzoate, andthe like; dihydroxy- and trihydroxy-benzoic acid phenyl esters;dihydroxy-, trihydroxy-, and tetrahydroxy- diphenyl sulfides such as4,4'dihydroxydiphenyl sulfide; dihydroxydiphenyl sulfones; anddihydroxy- and trihydroxy- phenyl naphthyl ketones such as2,3,4-trihydroxyphenyl naphthyl ketone; and the like. Examples ofcompounds of general formula (I) where at least one R_(a) radical ishalogen or lower alkyl include 2,4-dihydroxy-3,5-dibromobenzophenone;5-bromo-2,4-dihydroxybenzoic acid and esters;2,4,2',4-tetrahydroxy-3,5,3',5'-tetrabromodiphenyl;4,4'-dihydroxy-2,2'dimethyl-5,5'-di-tert.-butyl diphenyl;4,4'-dihydroxy-2,2'dimethyl-5,5'-di-tert.-butyl diphenyl sulfide;2,4,2',4'-tetrahydroxy-3,5,3'5'-tetrabromodiphenyl sulfone; and thelike.

The preferred class of phenolic compounds of general formula (I) are thehydroxyl-bearing benzophenones and the especially preferred compoundsare the trihydroxybenzophenones.

Among the phenolic compounds represented by general formula (II) are:dihydroxynaphthalenes such as 1,2-dihydroxynaphthalene;1,4-dihydroxynaphthalene; 1,5-dihydroxynaphthalene;1,6-dihydroxynaphthalene; 1,7-dihydroxynaphthalene;1,8-dihydroxynaphthalene; 2,3-dihydroxynaphthalene;2,6-dihydroxynaphthalene; 2,7-dihydroxynaphthalene, and the like;dihydroxydinaphthylmethanes such as 2,2'dihydroxydinaphthylmethane, andthe like. The dihydroxynaphthylenes are preferred. The hydroxyl groupsof the dihydroxynaphthylenes may be either on the same nucleus or ondifferent nuclei of the naphthalene moiety.

Among the phenolic compounds represented by general formula (III) are

bis-(3-benzoyl-4,5,6-trihydroxphenyl)-methane;

bis-(3-acetyl-4,5,6-trihydroxyphenyl)-methane;

bis-(3-propionyl-4,5,6-trihydroxyphenyl)-methane;

bis-(3-butyryl-4,5,6-trihydroxyphenyl)-methane;

bis-(3-hexanoyl-4,5,6- trihydroxyphenyl)-methane;

bis-(3-heptanoyl-4,5,6-trihydroxyphenyl)-methane;

bis-(3-decanoyl-4,5,6-trihydroxyphenyl)-methane;

bis-(3-octadecanoyl-4,5,6-trihydroxyphenyl)-methane; and the like.

The organic acid halides which may be used to modify the Diazo 1 estercompounds may be represented by the formula:

    W--R.sub.3 ,

wherein W is ##STR54## or --SO₂ --V, V is halogen, preferably Cl or Br,and R₃ is alkyl, aryl, substituted alkyl or substituted aryl; the alkylradicals R₃ may be straight-chain or branched and may be substitutedwith halogen atoms, preferably Br or Cl, or lower alkoxy groups having1-4 carbon atoms, preferably the alkyl radicals have 1-20 carbon atoms;the aryl radicals R₃ are preferably mononuclear and may be substitutedwith lower alkyl or alkoxy groups having 1-4 carbon atoms or withhalogen atoms, preferably Br or Cl, preferably the aryl radicals have 6to 10 carbon atoms, phenyl radicals are especially preferred: compoundsin which R₃ is an alkyl radical are particularly preferred and compoundsin which the alkyl radical is lower alkyl radical having 1-6 carbonatoms are especially preferred.

Among the organic acid halides represented by the above formula arealkyl sulfonyl halides such as methanesulfonyl chloride, ethanesulfonylchloride, propanesulfonyl chloride, n-butanesulfonyl chloride,dodecanesulfonyl chloride, and the like; arylsulfonyl chlorides such asbenzenesulfonyl chloride, naphthalenesulfonyl chlorides, and the like;acyl halides such as acetyl, chloride, butanoyl chloride, valerylchloride, benzoyl chloride, benzoyl bromide, naphthoyl chlorides, andthe like.

The preferred organic halides are lower alkyl sulfonyl halides and loweralkyl acyl halides having 1-6 carbon atoms, and benzenesulfonyl halidesand benzoyl halides. These acid halides may be substituted orunsubstituted.

The crosslinking compound is a compound, which when in the presence ofthat amount and strength of the acid generated when the diazide isexposed to actinic radiation, is capable of crosslinking the foregoingnovolak, or polyvinyl phenol resin. This occurs upon the application ofsufficient heat to diffuse the acid to the crosslinking component butless heat than will decompose the diazide. The general class of suchcompounds are those capable of forming a carbonium ion under theforegoing acid and heat conditions.

Crosslinkers suitable for use in the present invention have the generalformula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO₂,--O--CO₂ --, --CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl,cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄are independently H, C₁ -C₄ -alkyl or substituted or unsubstitutedphenyl and n ranges from 1 to 3 and m ranges from 0-3, provided that n+mis greater than 1. In the preferred embodiment the crosslinking compoundhas the formula ##STR55## wherein R₁, R₄, R₅, R₆ are independently H,(C₁ -C₆) alkyl, (C₃ -C₆) cycloalkyl, aryl, arylalkyl or OR₂ ; and

R₂, R₃ are independently H, (C₁ -C₆) alkyl, (C₃ -C₆) cycloalkyl, aryl,or arylalkyl.

The preferred compounds are dimethylol paracresol as described in U.S.Pat. No. 4,404,272 which is incorporated by reference, and its ether andester derivatives including benzene,1-methoxy-2,6-bis(hydroxymethyl-4-methyl; phenol,2,6-bis(methoxymethyl)-4-methyl; and benzene,1-methoxy-2,6-bis(methoxymethyl-4-methyl; methyl methoxy diphenyl ether,melamine formaldehyde resins and compounds and alkylated analoguesthereof having 1 to about 3 monomer units such as those typically soldunder the trade names Cymel from American Cyanamid and Resimene from theMonsanto Company, for example hexamethylol melamine hexamethyl ether,and epoxy cresol novolak resin.

The epoxy cresol novolak resins have the general formula ##STR56##

The photosensitive composition is formed by blending the ingredients ina suitable solvent composition. In the preferred embodiment the resin ispreferably present in the overall composition in an amount of from about75% to about 99% based on the weight of the solid, i.e. non-solventparts of the composition. A more preferred range of resin would be fromabout 80% to about 90% and most preferably from about 82% to about 85%by weight of the solid composition parts. The diazide is preferablypresent in an amount ranging from about 1% to about 25% based on theweight of the solid, i.e., non-solvent parts of the composition. A morepreferred range of the diazide would be from about 1% to about 20% andmore preferably from about 10% to about 18% by weight of the solidcomposition parts. The crosslinker is preferably present in an amountranging from about 0.5% to about 20% based on the weight of the solid,i.e. non-solvent parts of the composition. A more preferred range wouldbe from about 1% to about 10% and most preferably from about 3% to about6% by weight of the solid composition parts. In manufacturing thecomposition the resin, crosslinker and diazide are mixed with suchsolvents as the propylene glycol alkyl ether acetate, butyl acetate,xylene, ethylene glycol monoethyl ether acetate, and propylene glycolmethyl ether acetate, among others.

Additives such as colorants, dyes, anti-striation agents, levelingagents, plasticizers, adhesion promoters, speed enhancers, solvents andsuch surfactants as non-ionic surfactants may be added to the solutionof resin, sensitizer, cross-linker and solvent before the solution iscoated onto a substrate.

Examples of dye additives that be used together with the photoresistcompositions of the present invention include Methyl Violet 2B (C. I.No. 42535), Crystal Violet (C. I. 42555), Malachite Green (C. I. No.42000), Victoria Blue B (C. I. No. 44045) and Neutral Red (C. I. No.50040) at one to ten percent weight levels, based on the combined weightof the solid parts of the composition. The dye additives help provideincreased resolution b inhibiting back scattering of light off thesubstrate.

Anti-striation agents may be used up to five percent weight level, basedon the combined weight of solids.

Plasticizers which may be used include, for example, phosphoric acidtri-(beta-chloroethyl)-ester; stearic acid; dicamphor; polypropylene;acetal resins; phenoxy resins; and alkyl resins at one to ten percentweight levels, based on the combined weight of solids. The plasticizeradditives improve the coating properties of the material and enable theapplication of a film that is smooth and of uniform thickness to thesubstrate.

Adhesion promoters which may be used include, for example,beta-(3,4-epoxy-cyclohexyl)-ethyltrimethoxysilane;p-methyldisilane-methyl methacrylate; vinyltrichlorosilane; andgamma-amino-propyl triethoxysilane up to a 4 percent weight level, basedon the combined weight of solids.

Speed enhancers that may be used include, for example, picric acid,nicotinic acid or nitrocinnamic acid at a weight level of up to 20percent, based on the combined weight of resin and solids. Theseenhancers tend to increase the solubility of the photoresist coating inboth the exposed and unexposed areas, and thus they are used inapplications when speed of development is the overriding considerationeven though some degree of contrast may be sacrificed; i.e., while theexposed areas of the photoresist coating will be dissolved more quicklyby the developer, the speed enhancers will also cause a larger loss ofphotoresist coating from the unexposed areas.

The coating solvents may be present in the overall composition in anamount of up to 95% by weight of the solids in the composition.

Non-ionic surfactants that may me be used include, for example,nonylphenoxy poly(ethyleneoxy) ethanol; octylphenoxy(ethyleneoxy)ethanol; and dinonyl phenoxy poly (ethyleneoxy) ethanol at up to 10percent weight, based on the combined weight of solids.

The prepared resist solution can be applied to a substrate by anyconventional method used in the photoresist art, including dipping,spraying, whirling and spin coating. When spin coating, for example, theresist solution can be adjusted as to the percentage of solids contentin order to provide coating of the desired thickness given the type ofspinning equipment utilized and the amount of time allowed for thespinning process. Suitable substrates include silicon, aluminum orpolymeric resins, silicon dioxide, doped silicon dioxide, siliconnitride, tantalum, copper, polysilicon, ceramics and aluminum/coppermixtures.

The photoresist coating produced by the above described procedure areparticularly suitable for application to thermally grown silicon/silicondioxide-coated wafers such as are utilized in the production ofmicroprocessors and other miniaturized integrated circuit components. Analuminum/aluminum oxide wafer can be used as well. The substrate mayalso comprise various polymeric resins especially transparent polymerssuch as polyesters.

After the resist composition solution is coated onto the substrate, thesubstrate is temperature treated at approximately 20° C. to 100° C. Thetemperature treatment is selected in order to reduce and control theconcentration of residual solvents in the photoresist while not causingsubstantial thermal degradation of the photosensitizer. In general onedesires to minimize the concentration of solvents and thus this firsttemperature treatment is conducted until substantially all of thesolvents have evaporated and a thin coating of photoresist composition,on the order of a micron in thickness, remains on the substrate. Thistreatment is normally conducted at temperatures in the range of fromabout 20° C. to 100° C. In a preferred embodiment the temperature isconducted at from about 50° C. to 90° C. A more preferred range is fromabout 70° C. to 90° C. This treatment is conducted until the rate ofchange of solvent removal becomes relatively insignificant. Thetemperature and time selection depends on the resist properties desiredby the user as well as equipment used and commercially desired coatingtimes. Commercially acceptable treatment times for hot plates treatmentare those up to about 3 minutes, more preferably up to about 1 minute.In one example, a 30 second treatment at 90° C. is useful. The coatingsubstrate can then be exposed to actinic radiation, especiallyultraviolet radiation, in any desired pattern, produced by use ofsuitable masks, negatives, stencils, templates, etc. in a manner wellknown to the skilled artisan. The resist is then subjected to a postexposure second baking or heat treatment of from about 95° C. to about160° C. preferably 95° C. to 150° C., more preferably 112° C. to 120° C.This heating treatment may be conducted with a hot plate system for fromabout 10 seconds to the time necessary to crosslink the resin. Thisnormally ranges from about 10 seconds to 90 seconds, more preferablyfrom about 30 seconds to about 90 seconds and most preferably from about15 to 45 seconds. Durations for longer than 90 seconds are possible butdo not generally provide any additional benefit. The time selecteddepends on the choice of composition components and the substrate used.Heating diffuses the generated acid to the crosslinking component. Thebaking treatment also converts the diazide to a carboxylic acidcontaining compound, for example indene carboxylic acid, which issoluble in aqueous alkali solutions.

The selection of the first and second heat treatment temperatures andfirst and second heat treatment times may be selected and optimized bythe properties which are desired by the end user.

After the post exposure bake, an optional overall flood exposure toactinic radiation may be used. Such is preferably in the range of fromabout 200 to about 500 nm.

The exposed resist-coated substrates are next substantially immersed ina suitable developing solution. The solution is preferably agitated, forexample, by nitrogen burst agitation. The substrates are allowed toremain in the developer until all, or substantially all, of the resistcoating has dissolved from the exposed areas. Suitable developersinclude aqueous alkaline solutions such as those including sodiumhydroxide, and tetramethyl ammonium hydroxide as are well known in theart.

After removal of the coated wafers from the developing solution, anoptional post-development heat treatment or bake may be employed toincrease the coating's adhesion and chemical resistance to etchingsolutions and other substances. The post-development heat treatment cancomprise the oven baking of the coating and substrate below thecoating's softening point. In industrial application, particularly inthe manufacture of microcircuitry units on silicon/silicon dioxide-typesubstrates, the developed substrates may be treated with a buffered,hydrofluoric acid base etching solution. The resist compositions of thepresent invention are resistant to acid-base etching solutions andprovide effective protection for the unexposed resist-coating areas ofthe substrate.

The following specific examples will provide detailed illustrations ofthe methods of producing and utilizing compositions of the presentinvention. These examples are not intended, however, to limit orrestrict the scope of the invention in any way and should not beconstrued as providing conditions, parameters or values which must beutilized exclusively in order to practice the present invention.

Preparation of Photosensitizer Compositions

The preparation of naphthoquinonediazide photosensitizers is describedin U.S. Pat. Nos. 3,046,118, 3,106,645 and 4,397,937, which are herebyincorporated by reference. The photosensitizer compositions of thisinvention may be obtained by condensing the desirednaphthoquinonediazide sulfonyl halides and/or organic acid halide with aphenolic compound which has more than one hydroxyl group in the presenceof an acid scavenger. The resulting sensitizer composition may bepurified as desired.

Solvents for the reaction may include, but are not limited to, acetone,p-dioxane, tetrahydrofuran, methylene chloride, pyridine, or the like.

The acid scavenger may be inorganic, such as sodium carbonate, or thelike, or organic, such as sodium salts of weak acids, tertiary aminessuch as triethyl amine, pyridines, or the like.

EXAMPLE 1

A ten mole percent methanesulfonyl-modified2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acidtriester is prepared. 23.0 grams of 2,3,4-trihydroxybenzophenone and72.6 qrams of 1,2-naphthoquinonediazide-4-sulfonyl chloride (Diazo) arestirred together in 350 ml acetone. 3.6 grams of methanesulfonylchloride are added in. 36.4 grams of triethylamine are slowly dropped inwhile maintaining an internal temperature of about 30° C. The reactionmixture is cooled to 15° C., treated with charcoal and diatomaceousearth, filtered, washed with 350 ml acetone, and drowned in 3.5 litersof 1 normal hydrochloric acid. The product is filtered off, washed withwater, and dried in an air oven at 40° C. The yield obtained is 85.9grams, 97.5% of theory.

The product thusly obtained may be purified as desired.

EXAMPLE 2

A ten mole percent Diazo 2-modified2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acidtriester is prepared. 23.0 grams of 2,3,4-trihydroxybenzophenone and72.6 grams of 1,2-naphthoquinonediazide-4-sulfonyl chloride (Diazo 1)are stirred together in 350 ml acetone. 8.06 grams of1,2-naphthoquinonediazide-5-sulfonyl chloride (Diazo 2) are added in.36.4 grams of triethylamine are slowly dropped in while maintaining aninternal temperature of about 30° C. The reaction mixture is cooled to15° C., treated with charcoal and diatomaceous earth, filtered, washedwith 350ml acetone, and drowned in 3.5 liters of 1 normal hydrochloricacid. The product is filtered off, washed with water, and dried in anair oven at 40° C. The yield obtained is 92.3 grams which is 99.6percent of theory.

The product thusly obtained may be purified as desired.

The method of synthesis shown in these examples are not the only way tomake such photosensitizer compositions, as those skilled in the art mayobtain comparable products by simply varying solvents, bases or reactionconditions.

Preparation and Use of Photoresist EXAMPLE 3

The photoresist is made up of a solution containing 5% of solids ofdimethylol paracresol, 12% of solids of a photosensitizer compositionprepared according to Example 1, and 83% of solids of cresol novolacresin in propylene glycol monomethyl ether acetate.

Using this formulation silicon wafer is coated at 4,000 rpm and thensoft-baked in a recirculating forced air oven at 90° C. for 30 minutes.Actinic exposure is applied using the Perkin Elmer 220 Micralign alignerthrough a quartz photomask containing open patterns of graduated opticaldensity giving nominally 1 to 100% transmission. 100% intensitycorresponds to 50 mJ/cm² as determined by an OAI radiometer forwavelengths between 365 and 436 nm. After exposure the wafer is hardbaked on a MTI Inc. hot plate at 120° C. for 60 seconds. An image is nowvisible to the unaided eye under yellow safelight.

After developing the exposed and hard baked wafers in AZ 440 MIFDeveloper available from AZ Photoresists Group of Hoechst CelaneseCorporation, Somerville, New Jersey (a solution of tetramethylammoniumhydroxide with added surfactant) in an immersion mode for 90 secondswith slight agitation, the wafers are DI water rinsed and spin dry.Examination of the cleaned and uncleaned portions of the wafer withrespect to the nominal incident energy shows an insufficient number ofdata points between complete cleaning and essentially complete retentionof photoresist to provide an exact calculation of photospeed andcontrast. Both seem to have values near ten as normally calculated.Small line and space patterns embedded in the open areas are seen under10× magnification to be completely opened.

EXAMPLE 4

The photoresist is made up of a solution containing 5% of solids ofdimethylol paracresol, 6% of solids of a photosensitizer compositionprepared according to Example 2, and 89% of solids of cresol novolacresin in propylene glycol monomethyl ether acetate.

Using this formulation silicon wafers are coated at 4,000 rpm and thensoft-baked in a vented convection oven at 90° C. for 30 minutes. Actinicexposure is applied using the Perkin Elmer 220 Micralign aligner througha glass photomask containing a resolution test pattern. Using aperature#4, the scan speeds are varied between 260 and 520 arbitrary energyunits. These different scan speeds (each scan speed represents adifferent experiment) corresponds to between 14 and 7 mJ/cm²respectively as determined by an OAI radiometer for wavelengths between365 and 436 nm. The photomask consists of a resolution test patternwhere single line and equal line and spaces are represented. The widthof these features varies between 1.0 and 3.0 um in 0.25 um increments.After exposure the wafers are hard baked sequentially on a MTI Inc. hotplate at temperatures ranging from 105° C. to 155° C. for up to 60seconds. A relief image is now observable when the wafers are placedunder an optical microscope with monochromatic 520 nm illumination.

EXAMPLE 5

The photoresist is made up of a solution containing 5% of solids ofdimethylolparacresol, 6% of solids of 2,3,4-trihydroxy-benzophenonereacted with 1,2-naphthaquinone 2-diazide-4-sulfonic acid and 1,2naphthoquinone-2-diazide-5-sulfonic acid and 89% of cresol novolac resinin propylene glycol monomethyl ether acetate.

Using this formulation silicon wafers were coated at 4000 rpm and thensoft-baked on a hot plate at 90° C. for 60 seconds. Actinic exposure isapplied using a broad band exposure source through a glass photomask.The mask has both zones of differing optical density and a pattern oflines and spaces. After exposure, the wafer is hard baked on a hot plateat 120° C. for 60 seconds. The photoresist is developed in a 0.36 Nsolution of tetramethylammonium hydroxide. A negative image is obtained.In addition, a plot of film thickness remaining against the log ofexposure dose is constructed. The slope of this is contrast and theintercept is the photospeed. This example gives a contrast of 8.3 and aphotospeed of 12.2 mJcm⁻².

EXAMPLE 6

A photoresist is made up of a solution containing 5% of solids ofdimethylolparacresol, 6% of solids of 2,3,4-trihydroxy-benzophenonereacted with 1,2 naphthoquinone-2-diazide-4-sulfonic acid and 1,2naphthoquinone-2-diazide-5-sulfonic acid, and 89% of cresol novolacresin in propylene glycol monomethyl ether acetate.

Using this formulation silicon wafers are coated at 4000 rpm and thensoft-baked on a hot plate at 90° C. for 60 seconds. Actinic exposure isapplied using a broad band exposure source through a glass photomask.The mask has both zones of differing optical density and a pattern oflines and spaces. After exposure the wafer is hard baked on a hot plateat 120° C. for 60 seconds. The photoresist is flood exposed with 1000mJcm⁻² then developed in a 0.22 N solution of tetramethylammoniumhydroxide. A negative image is obtained. In addition, a plot of filmthickness remaining against log exposure dose is constructed. The slopeof this is contrast and the intercept is the photospeed. This examplegives a contrast of 10.7 and a photospeed of 12.5 mJcm⁻².

EXAMPLE 7

A photoresist is made up of a solution containing 5% of solids ofdimethylolparacresol, 6% of solids of 2,3,4-trihydroxy-benzophenonereacted with 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2naphthoquinone-2-diazide-5-sulfonic acid and 89% ofpoly(p-hydroxystyrene) resin in propylene glycol monomethyl etheracetate.

Using this formulation, silicon wafers are coated at 4000 rpm and thensoft-baked on a hot plate at 90° C. for 60 seconds. Actinic exposure isapplied using a broad band exposure source through a glass photomask.The mask has both zones of differing optical density and a pattern oflines and spaces. After exposure the wafer is hard baked on a hot plateat 120° C. for 60 seconds. The photoresist is developed in a 0.18 Nsolution of tetramethylammonium hydroxide. A negative image is obtained.In addition a plot of film thickness remaining against the log ofexposure dose is constructed. The slope of this is the contrast and theintercept is the photospeed. This example gives a contrast of 11.1 and aphotospeed of 2.4 mJcm⁻².

EXAMPLE 8

A photoresist is made up of a solution containing 5% of solids ofdimethylolparacresol, 6% of solids of 2,3,4-trihydroxy-benzophenonereacted with 1,2-naphthoquinone-2-diazide-4-sulfonic acid and1,2-naphthoquinone-2-diazide-5-sulfonic acid and 89% ofpoly(p-hydroxystyrene) in propylene glycol monomethyl ether acetate.

Using this formulation silicon wafers are coated at 4000 rpm and thensoft-baked on a hot plate at 90° C. for 60 seconds. Actinic exposure isapplied using a broad band exposure source through a glass photomask.The mask has both zones of differing optical density and a pattern oflines and spaces. After exposure the wafer is hard baked on a hot plateat 120° C. for 60 seconds. The photoresist is flood exposed with 1000mJcm⁻² and the photoresist is developed in a 0.18 N solution oftetramethylammonium hydroxide. A negative image is obtained. Inaddition, a plot of film thickness remaining against the log of exposuredose is constructed. The slope of this is contrast, and the intercept isthe photospeed. This example gives a contrast of 10 and a photospeed of3 mJcm⁻².

What is claimed is:
 1. A process for preparing and using a negativeworking photographic element which comprises in order:a) forming acomposition which comprises in admixturei) from about 1% to about 25%based on the weight of the solid parts of the composition of aphotosensitive compound represented by the general formulae (1), (2) or(3): ##STR57## wherein R is H, --X--R_(b) or ##STR58## X is a singleC--C bond, --O--, --S--, --SO₂ --, ##STR59## n is 1 or 2, R_(a) is H,--OH, --OY, --OZ, halogen or lower alkyl, with at least one R_(a)radical being --OY and at least one thereof being --OZ, R_(b) is H,alkyl, aryl, substituted alkyl, or substituted aryl; ##STR60## wherein Ris H, or ##STR61## Rc is H, --OH, --OY or --OZ, with at least one R_(c)radical being --OY and at least one thereof being --OZ; and ##STR62##wherein R₂ is H, alkyl, aryl, substituted alkyl, or substituted aryl,R_(d) is --OH, --OY or --OZ with at least one R_(d) radical --OY and atleast one thereof being --OZ; wherein Y is 1,2-naphthoquinonediazide4-sulfonyl and Z is 1,2-naphthoquinonediazide-5-sulfonyl or --W--R₃,where W is ##STR63## or --SO₂ --, and R₃ is alkyl, aryl, substitutedalkyl or substituted aryl; ii) from about 75% to about 99% based on theweight of the solid parts of the composition of a polyvinyl phenolresin; and iii) from about 0.5% to about 20% based on the weight of thesolid parts of the composition of a crosslinking compound which, when inthe presence of that amount and strength of the acid generated when saiddiazide is exposed to actinic radiation, is capable of crosslinking saidresin under the application of the heating conditions of step (e), saidcrosslinking compound has the formula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted monoclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ --C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO₂ --,--CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl, cycloalkyl,substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄ areindependently H, C₁ -C₄ -alkyl or substituted or unsubstituted phenyland n ranges from 1 to 3 and m ranges from 0-3, provided that n+m isgreater than 1; and iv) sufficient solvent to dissolve the foregoingcomposition components; and b) coating said composition on a substrate;and c) heating said coated substrate at a temperature of from about 20°C. to about 100° C. until substantially all of said solvent is driedoff; and d) imagewise exposing said composition to actinic, electronbeam, ion beam or x-ray radiation; and e) heating said coated substrateat a temperature of at least about 95° C. to about 160° C. for fromabout 10 seconds or more to crosslink said resin; then optionally floodexposing the composition overall to actinic radiation in the range offrom about 200 to about 500 nm in an amount sufficient to react saidcoating; and f) removing the radiation unexposed non-image areas of saidcomposition from step d) with a developer.
 2. The process of claim 1wherein the crosslinking compound has the formula ##STR64## wherein R₁,R₄, R₅, R₆ are independently H, (C₁ -C₆) alkyl, (C₃ -C₆) cycloalkyl,aryl, arylalkyl or OR₂ ; and R₂, R₃ are independently H, (C₁ -C₆) alkyl,(C₃ -C₆) cycloalkyl, aryl, or arylalkyl.
 3. The process of claim 1wherein said crosslinker is dimethylol paracresol or methyl methoxydiphenyl ether.
 4. The process of claim 1 wherein said crosslinkercompound is one or more compounds selected from the group consisting ofbenzene, 1-methoxy-2,6-bis(hydroxymethyl-4-methyl-; phenol,2,6-bis(methoxymethyl)-4-methyl-; and benzene,1-methoxy-2,6-bis(methoxymethyl)-4-methyl-.
 5. The process of claim 1wherein said solvent comprises propylene glycol alkyl ether acetate. 6.The process of claim 1 wherein said substrate is selected from the groupconsisting of silicon, aluminum or polymeric resins, silicon dioxide,doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon,ceramics and aluminum/copper mixtures.
 7. The process of claim 1 whereinsaid composition further comprises one or more compounds selected fromthe group consisting of colorants, dyes, anti-striation agents, levelingagents, plasticizers, adhesion promoters, speed enhancers, andsurfactants.
 8. The process of claim 1 wherein said developer is anaqueous alkaline solution.
 9. The process of claim wherein after step(e) said coated substrate is overall exposed to actinic radiation offrom about 200 to about 500 nm.
 10. A process for preparing and using anegative working photographic element which comprises in order:a)forming a composition which consists essentially of in admixturei) fromabout 1% to about 25% based on the weight of the solid parts of thephotosensitive compositions comprising the condensation product of:(I) aphenolic compound selected form the group consisting of: ##STR65##wherein R is H, or --X--R_(b) ; or ##STR66## R_(a) is H, --OH, halogenor lower alkyl, with at least two and not greater than six R_(a)radicals being --OH, X is a single C--C bond, --O--, --S--, --SO₂ --,##STR67## n is 1 or 2, R_(b) is H, alkyl, aryl, substituted alkyl orsubstituted aryl; ##STR68## wherein R₂ is H or ##STR69## Rc is H, or--OH with at least two R_(c) radicals being --OH; and ##STR70## whereinR₂ is H, alkyl, aryl, substituted alkyl, or substituted aryl; (II) a1,2-naphthoquinonediazide-4-sulfonic acid (Diazo 1); and (III) a1,2-naphthoquinonediazide-5-sulfonic acid (Diazo 2); and/or an organicacid halide represented by the formula:

    W--R.sub.3

wherein W is ##STR71## or --SO₂ --V, V is halogen, R3 is alkyl, aryl,substituted alkyl, or substituted aryl; wherein the molar ratio of theamount of Diazo 1 reacted to the amount of Diazo 2 and/or organic acidreacted is in the range of from about 1:1 to about 39:1; ii) from about75% to about 99% based on the weight of the solid parts of thecomposition of a novolak resin; and iii) from about 0.5% to about 20%based on the weight of the solid parts of the composition of acrosslinking compound which, when in the presence of that amount andstrength of the acid generated when said diazide is exposed to actinicradiation, is capable of crosslinking said resin under the applicationof the heating conditions of step (e), said crosslinking compound hasthe formula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO₂,--O--CO₂ --, --CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl,cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄are independently H, C₁ -C₄ -alkyl or substituted or unsubstitutedphenyl and n ranges from 1 to 3 and m ranges from 0-3, provided that n+mis greater than 1; and iv) sufficient solvent to dissolve the foregoingcomposition components; and b) coating said composition on a substrate;and c) heating said coated substrate at a temperature of from about 20°C. to about 100° C. until substantially all of said solvent is driedoff; and d) imagewise exposing said composition to actinic, electronbeam, ion beam or x-ray radiation; and e) heating said coated substrateat a temperature of at least about 95° C. to about 160° C. for fromabout 10 seconds or more to crosslink said resin; then flood exposingthe composition overall to actinic radiation in the range of from about200 to about 500 nm in an amount sufficient to react said coating; andf) removing the radiation unexposed non-image areas of said compositionfrom step d) with a developer.
 11. A process for preparing and using anegative working photographic element which comprises in order:a)forming a composition which consists essentially ofi) from about 1% toabout 25% based on the weight of the solid parts of the photosensitivecompositions comprising the condensation product of:(I) a phenoliccompound selected from the group consisting of: ##STR72## wherein R isH, --X--R_(b) or ##STR73## R_(a) is H, --OH, halogen or lower alkyl,with at least two and not greater than six R_(a) radicals being --OH, Xis a single C--C bond, --O--, --S--, --SO₂ --, ##STR74## n is 1 or 2,R_(b) is H, alkyl, aryl, substituted alkyl or substituted aryl;##STR75## wherein R₂ is H, or ##STR76## Rc is H, or --OH with at leasttwo R_(c) radicals being --OH; and ##STR77## wherein R₂ is H, alkyl,aryl, substituted alkyl, or substituted aryl; (II) a1,2-naphthoquinonediazide-4-sulfonic acid (Diazo 1); and (III) a1,2-naphthoquinonediazide-5-sulfonic acid (Diazo 2); and/or an organicacid halide represented by the formula:

    W--R.sub.3

wherein W is ##STR78## or --SO₂ --V, V is halogen, R3 is alkyl, aryl,substituted alkyl, or substituted aryl; wherein the molar ratio of theamount of Diazo 1 reacted to the amount of Diazo 2 and/or organic acidreacted is in the range of from about 1:1 to about 39:1; ii) from about75% to about 99% based on the weight of the solid parts of thecomposition of a polyvinyl phenol resin; and iii) from about 0.5% toabout 20% based on the weight of the solid parts of the composition of acrosslinking compound which, when in the presence of that amount andstrength of the acid generated when said diazide is exposed to actinicradiation, is capable of crosslinking said resin under the applicationof the heating conditions of step (e), said crosslinking compound hasthe formula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --,--CO--, CO₂,--O--CO₂ --, --CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl,cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄are independently H, C₁ -C₄ -alkyl or substituted or unsubstitutedphenyl and n ranges from 1 to 3 and m ranges from 0-3, provided that n+mis greater than 1; and iv) sufficient solvent to dissolve the foregoingcomposition components; and b) coating said composition on a suitablesubstrate; and c) heating said coated substrate at a temperature of fromabout 20° C. to about 100° C. until substantially all of said solvent isdried off; and d) imagewise exposing said composition to actinic,electron beam, ion beam or x-ray radiation; and e) heating said coatedsubstrate at a temperature of at least about 95° C. to about 160° C. forfrom about 10 seconds or more to crosslink said resin; then optionallyflood exposing the composition overall to actinic radiation in the rangeof from about 200 to about 500 nm in an amount sufficient to react saidcoating; and f) removing the unexposed non-image areas of saidcomposition from step d) with a suitable developer.
 12. A process forpreparing and using a negative working photographic element whichcomprises in order:a) forming a composition which consists essentiallyof in admixture:i) from about 1% to about 25% based on the weight of athe solid parts of the composition of a photosensitive compositioncomprising the condensation product of:I. A phenolic compound having thestructure: ##STR79## wherein: R_(a) is H, OH, halogen or lower alkyl,with at least two and not greater than six R_(a) radicals being OH, andX is a single C--C bond, --O--, --S--, --SO₂ --, ##STR80## n is 1 or 2;II. A 1,2 naphthoquinonediazide-4-sulfonic acid (Diazo I), and III. A1,2 naphthoquinonediazide-5-sulfonic acid (Diazo II) or an organic acidof the formula W--R₃, wherein W is ##STR81## or --SO₂ --V, V is halogenand R₃ is alkyl, aryl, substituted alkyl or substituted aryl; whereinthe molar ratio of the amount of Diazo I reacted to the amount of DiazoII and/or organic acid reacted is the range of from about 1:1 to about39:1; ii) from about 75% to about 99% based on the weight of the solidparts of the composition of a novolak resin; and iii) from about 0.5% toabout 20% based on the weight of the solid parts of the composition of acrosslinking compound which, when in the presence of that amount andstrength of the acid generated when said diazide is exposed to actinicradiation, is capable of crosslinking said resin under the applicationof the heating conditions of step (e), said crosslinking compound hasthe formula ##STR82## wherein R₁, R₄, R₅, R₆ are independently H, (C₁-C₆)alkyl, (C₃ -C₆)cycloalkyl, aryl, arylalkyl or OR₂ ; and R₂, R₃ areindependently H, (C₁ -C₆)alkyl, (C₃ -C₆)cycloalkyl, aryl or arylalkyl;and iv) sufficient solvent to dissolve the foregoing compositioncomponents; and b) coating said composition on a substrate; and c)heating said coated substrate at a temperature of from about 20° toabout 100° C. until substantially all of said solvent is dried off; andd) imagewise exposing said composition to actinic, electron beam, ionbeam or x-ray radiation; and e) heating said coated substrate at atemperature of at least about 95° C. to about 160° C. for about 10seconds or more to crosslink said resin; then flood exposing thecomposition overall to actinic radiation in the range of from about 200to about 500 nm in an amount sufficient to react said coating; and f)removing the unexposed non-image areas of said composition from step d)with a developer.
 13. A process for preparing and using a negativeworking photographic element which comprises in order:a) forming acomposition which consists essentially of in admixturei) from about 1%to about 25% based on the weight of the solid parts of the compositionof a photosensitive compound represented by the general formulae (1),(2) or (3): ##STR83## wherein R is H, --X--R_(b) or ##STR84## X is asingle C--C bond, --O--, --S--, --SO₂ --, ##STR85## n is 1 or 2, R_(a)is H, --OH, --OY, --OZ, halogen or lower alkyl, with at least one R_(a)radical being --OY and at least one thereof being --OZ, R_(b) is H,alkyl, aryl, substituted alkyl, or substituted alkyl, or substitutedaryl; ##STR86## wherein R is H, or ##STR87## Rc is H, --OH, --OY or--OZ, with at least one R_(c) radical being --OY and at least onethereof being --OZ; and ##STR88## wherein R₂ is H, alkyl, aryl,substituted alkyl, or substituted aryl, R_(d) is --OH, --OY or --OZ withat least one R_(d) radical --OY and at least one thereof being --OZ;wherein Y is 1,2-naphthoquinonediazide-4-sulfonyl and Z is1,2-naphthoquinonediazide-5-sulfonyl or --W--R₃, where W is ##STR89## or--SO₂ --, and R₃ is alkyl, aryl, substituted alkyl or substituted aryl;ii) from about 75% to about 99% based on the weight of the solid partsof the composition of a novolak resin; and iii) from about 0.5% to about20% based on the weight of the solid parts of the composition of acrosslinking compound which, when in the presence of that amount andstrength of the acid generated when said diazide is exposed to actinicradiation, is capable of crosslinking said resin under the applicationof the heating conditions of step (e), said crosslinking compound hasthe formula

    (R.sub.1 O--CHR.sub.3).sub.n --A--(CHR.sub.4 --OR.sub.2).sub.m

wherein A has the formula B or B--Y--B, wherein B is a substituted orunsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or aoxygen or sulfur containing heterocyclic compound, Y is a single bond,C₁ -C₄ -alkylene or -alkylenedioxy, the chains of which may beinterrupted by oxygen atoms, --O--, --S--, --SO₂ --, --CO--, CO₂,--CONH-- or phenylenedioxy, R₁ and R₂ are H, C₁ -C₆ -alkyl, cycloalkyl,substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄ areindependently H, C₁ -C₄ -alkyl or substituted or unsubstituted phenyland n ranges from 1 to 3 and m ranges from 0-3, provided that n+m isgreater than 1; and iv) sufficient solvent to dissolve the foregoingcomposition components; and b) coating said composition on a substrate;and c) heating said coated substrate at a temperature of from about 20°C. to about 100° until substantially all of said solvent is dried off;and d) imagewise exposing said composition to actinic, electron beam,ion beam or x-ray radiation; and e) heating said coated substrate at atemperature of at least about 95° C. to about 160° C. for from about 10seconds or more to crosslink said resin; then flood exposing thecomposition overall to actinic radiation in the range of from about 200to about 500 nm in an amount sufficient to react said coating; and f)removing the radiation unexposed non-image areas of said compositionform step d) with a developer.
 14. The process of claim 13 where thecrosslinking compound has the formula ##STR90## wherein R₁, R₄, R₅, R₆are independently H, (C₁ -C₆) alkyl, (C₃ -C₆) cycloalkyl, aryl,arylalkyl or OR₂ ; and R₂, R₃ are independently H, (C₁ -C₆) alkyl, (C₃-C₆) cycloalkyl, aryl, or arylalkyl.
 15. The process of claim 13 whereinsaid crosslinker is dimethylol paracresol or methyl methoxy diphenylether.
 16. The process of claim 13 wherein said crosslinker compound isone or more compounds selected form the group consisting of benzene,1-methoxy-2,6-bis(hydroxymethyl-4-methyl-; phenol,2,6-bis(methoxymethyl)-4-methyl-; and benzene,1-methoxy-2,6-bis(methoxymethyl)-4-methyl-.
 17. The process of claim 13wherein said solvent comprises propylene glycol alkyl ether acetate. 18.The process of claim 13 wherein said substrate is selected from thegroup consisting of silicon, aluminum or polymeric resins, silicondioxide, doped silicon dioxide, silicon nitride, tantalum, copper,polysilicon, ceramics and aluminum/copper mixtures.
 19. The process ofclaim 13 wherein said composition further comprises one or morecompounds selected form the group consisting of colorants, dyes,anti-striation agents, leveling agents, plasticizers, adhesionpromoters, speed enhancers, and surfactants.
 20. The process of claim 13wherein said developer is an aqueous alkaline solution.
 21. The processof claim 13 wherein after step (e) said coated substrate is overallexposed to actinic radiation of from about 200 to about 500 nm.